CN113906515A

CN113906515A - Unique identification and authentication of products

Info

Publication number: CN113906515A
Application number: CN202080041109.3A
Authority: CN
Inventors: N·温德哈布; K·伯顿; P·J·斯潘塞; J·米勒-阿尔贝斯; A·恩格尔; P·尼波特; R·阿利霍夫斯凯; J·柳比纳; C·布吕歇尔; C·登特勒; A·卡劳
Original assignee: Evonik Operations GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2019-06-04
Filing date: 2020-06-04
Publication date: 2022-01-07
Also published as: WO2020245280A8; EP4328880A3; EP3981016A1; IL288548A; CA3139309A1; BR112021024051A2; KR20220016267A; US20220326199A1; EP4328880A2; MX2021014845A; JP2022535119A; WO2020245280A1; EP3981016B1

Abstract

A method of positively identifying and authenticating a product for better identification of product counterfeiting and control of product piracy, the method comprising the method steps of: applying an identification substance blend comprising a paramagnetic phase to/in a product or identifying a product comprising an identification substance blend comprising a paramagnetic phase and having an ESR fingerprint allowing unambiguous identification of the product. Such ESR fingerprints can be measured in a simple manner, but are difficult to replicate or counterfeit. The method involves personalizable "femto tags" for femto ledgers, and forms an important interface known as the internet of things (IOT) application.

Description

Unique identification and authentication of products

Technical Field

The invention relates to a method for the unequivocal identification and authentication of products and to unequivocally identifiable and authenticatable products. The method thus provides a personalizable-femto tag "for femto ledgers and forms an important interface called internet of things (IOT) applications.

Background

Counterfeits and pirated copies of high-value products cause enormous economic losses each year. Counterfeits can also pose a high risk to many people's lives and limbs in the case of pharmaceuticals, food and beverage products, as well as suppliers and replacement parts in areas where safety is critical, such as the aviation and automotive industries.

Due to the manufacture of realistic reproductions of products, it is often difficult, if not even impossible, to distinguish the original product and the reproduction from each other. Especially in the case of plastics or paints, it is not possible or feasible to introduce a serial number or further information into the material of the product itself that allows the product to be identified.

According to the prior art, in order to prevent reproductions or counterfeits, as well as known security tags in the form of a set of tags, such as those used in the automotive industry, which are mounted on products and have various overt and covert security features, which are, for example, written into the information field with a high-resolution laser (DE 202007017753U 1). There are also holograms (DE 10030629 a1), lithographic prints with data carrier fields, bar codes and matrix codes (lithograms) which are installed on products and are capable of displaying information of a specific origin directly on the product at mutually independent information levels. A disadvantage of these known protection mechanisms is that these are manufactured with a high level of technical complexity and high costs and must generally be mounted on the product in a clearly visible manner.

US 2006/0054825 a1 discloses a method of identifying and authenticating different objects or substances, wherein the method utilizes a data processing system coupled to a spectrophotometric apparatus. The method is particularly characterized in that it comprises two phases: during an initial phase, a plurality of chemical markers are selected, then a combination of markers is assigned to and introduced into each object or substance, an authentication code is created, the authentication code is stored, and an identification code is assigned to the object or substance and also stored, then an assignment between the identification code and the authentication code is established. This is followed by an identification and authentication phase comprising theoretical identification of the object or substance by reading an identification code associated with the object or substance, spectrophotometric analysis of the object or substance and determination of an authentication code of the object or substance, authentication of the object or substance if the theoretical identification code corresponds to said authentication code, and finally issuing an approval signal if a protocol has been established or an alarm signal if the authentication code does not coincide with the identification code.

DE 4445004 a1 discloses compositions for delocalized labeling of articles and their preparation and use. The composition enables articles to be marked which makes it difficult to counterfeit or to improperly use or utilize such articles. Characterized in that it comprises chemical elements with a defined distribution of K α lines of 3.69keV to 76.315keV, wherein the physical properties of the substance or its elemental and/or quantitative composition are used as delocalized information not clearly visible to the naked eye.

DE 102008060675 a1 describes a method for unequivocally identifying and authenticating products to prevent duplication by using a marking, in which a powdery marking is incorporated into the material of the product to be protected, which marking comprises an inert carrier and a chemical element in a previously fixed element code consisting of a plurality of chemical elements and a sequence of previously defined codes with a defined arrangement of the chemical elements and a fixed relative concentration of the chemical elements. The support and the chemical element are thereby inseparably associated with one another, wherein the method comprises the following steps: (i) determining the chemical elements and their content in the marking material, (ii) comparing the values determined in step (i) with the previously fixed element code and the previously defined coding sequence.

US 2018/0335427 a1 describes the use of a label (tag) comprising at least one paramagnetic particle, wherein the at least one paramagnetic particle has a non-spherical form, a shape factor of greater than 1, and at least one unique and detectable chemical, wherein the at least one unique and detectable chemical is attached to the at least one paramagnetic particle, for tracking and identifying pharmaceutical and nutritional products. For example, unique and detectable chemical species attached to paramagnetic microparticles are analyzed by means of light absorption spectroscopy, raman spectroscopy, surface plasmon resonance, fluorescence, electrochemical detection, ion chromatography, and enzymatic color change chemistry.

Disadvantages of the above-described method include high technical complexity in the production of the marking and the verification of the product as a genuine product.

Therefore, there is a need for a simple, inexpensive and effective method of unambiguously identifying and authenticating a product in order to identify counterfeit or unauthorized copies.

Disclosure of Invention

The present invention is based on the surprising finding that: the electron resonance spectrum (ESR spectrum) can be detected firstly at a low level of complexity and secondly, by means of the combination of paramagnetic phases, a plurality of different ESR spectra, known as ESR fingerprint spectra (spectra), can be generated in particular and added to the product to be identified in the form of a substance blend (additure).

The invention therefore proposes a product having an identification substance blend comprising a paramagnetic phase and having an ESR fingerprint (spectrum) allowing the product to be identified unambiguously.

The paramagnetic phase of the identification substance blend may thereby be formed by one or more phases selected from the group consisting of:

paramagnetic centers, preferably selected from S radicals, preferably from ultramarine,

-an overall ordered state selected from ferromagnetic-, ferrimagnetic-and/or antiferromagnetic states, preferably from iron-oxygen compounds, more preferably from magnetite or a material with Fe-O phases,

selected from polymers having paramagnetic centers, preferably isolated radicals,

-molecular paramagnets, and

paramagnetic phase of mineral substances and/or salts, in particular selected from Al₂O₃、SiO₂Natural or artificially doped diamond or ZrO₂The paramagnetic phase of (a).

In one embodiment, the phase is selected from copper (II) sulfate, manganese (II) chloride, manganese (IV) oxide, zirconium (IV) oxide, lactose monohydrate, titanium dioxide, homopolymers and copolymers, especially (meth) acrylate copolymers, such as commercially available from Evonik Industries AG

E. L, RL, FL 30D, or polylactide-co-glycolides, as for example available under the trade name

Commercially available from Evonik Industries AG, natural ultramarine blue, D (-) -mannitol, diamond dust, magnesium oxide, jet black, D (+) -trehalose, microcrystalline cellulose such as commercially available Avicel PH-101, proteins, especially fermented and/or recombinant proteins such as triple helical collagen, and mixtures thereof. In one embodiment, in particular before the recording of the ESR fingerprint, the phases are activated by energy input, in particular by X-ray irradiation.

In one embodiment, the phase is a mixture of lactose monohydrate, MCC, natural ultramarine blue, diamond powder, copper (II) sulfate and magnesium oxide. In one embodiment, the phase is a mixture of natural ultramarine blue, diamond powder, copper (II) sulfate and magnesium oxide, preferably of equivalent mass. In one embodiment, a mixture of equivalent masses of natural ultramarine blue, diamond powder, copper (II) sulfate and magnesium oxide is diluted with lactose monohydrate and MCC in a weight ratio of 2/3:1/3 to 1/8:7/8, wherein lactose monohydrate and MCC are likewise used in equivalent masses to each other. In one embodiment, in particular before the recording of the ESR fingerprint, the mixture is activated by energy input, in particular by X-ray irradiation.

In one embodiment, the phase is included at 0.0005 to 50 wt.%, preferably 0.001 to 20 wt.%, more preferably 0.01 to 10 wt.% or 0.01 to 1 wt.%, based on the total weight of the sample analyzed. In one embodiment, the phase is included at 0.0005 to 0.1 wt.%, based on the total weight of the sample analyzed.

The mentioned materials preferably not only have the desired magnetic properties, but are also non-toxic and suitable for consumption, i.e. also for use in pharmaceuticals and food products.

The paramagnetic phase of the identification substance blend can be produced by methods comprising coating, blending, doping, sputtering, chemical radical generation, irradiation (in particular X-ray irradiation), and/or by printing methods. Printing methods may include letterpress, gravure, porous, screen, lithographic printing such as offset, digital, steel gravure, screen printing, electrophotographic (laser printing), powder printing methods such as Xerox and electrospray, electrospinning, precipitation, paper moulding or layering methods, e.g. screen printing, or direct imaging. Suitable starting materials and media for this purpose are, for example, pastes, inks, colorants, gases and vapors, lacquers, stencils, powders, solutions, melts, glasses and their physically active or chemically reactive forms.

To decode the information encoded in the ESR map, the resonance frequency, line shape, intensity, signal coupling and/or spatial variation in the ESR fingerprint may be evaluated here.

The ESR fingerprint identifying the substance blend is preferably mechanically and/or thermally stable. In this way, product identification is ensured even after mechanically and/or thermally demanding transport paths. Alternatively, however, for example in the case of pharmaceuticals or food and beverage products, a heat-sensitive ESR spectrum may be used to register a broken cooling chain, for example.

The product according to the invention can be, for example, a pharmaceutical or pharmaceutical product, a food or beverage product or a precursor or intermediate or a defined constituent thereof, such as, for example, a package, a blister pack, a container, such as a glass tube and a polymer tube, a syringe, an ampoule or a reservoir for liquids.

The product according to the invention may also be a textile, textile or leather product, a coin, a banknote, a security, a document, a certificate or cheque card or a chip card or a part thereof, such as a seal or a housing, or a gemstone or gemstone semi-gemstone, a medical product, an implant or graft, or a replacement part or supplier part of an industrial product.

The ESR fingerprint may encode the product itself, the manufacturer, the location of manufacture, the time of manufacture, and/or production specific data, such as the intended end use, rights such as licenses or geographic labels, authorities such as approval authorities, and the like.

The identification substance blend and accompanying ESR map may be selected identically for each individual product or for product batches.

The invention also proposes a method for producing a clearly identifiable product, comprising the method step of applying to the product a blend of an identification substance comprising a paramagnetic phase and having an ESR fingerprint allowing the product to be clearly identified.

The paramagnetic phase of the identification substance blend can be produced here by processes comprising coating, blending, doping, sputtering, chemical radical generation and/or irradiation (in particular X-ray irradiation), printing, embossing, melting, extrusion, pressing, pelletizing, spheronization, spray drying, additive manufacturing (3D printing), thermal transfer, thermal embossing, laser methods, inkjet printing and holographic printing.

The invention also provides a method for product authentication, which comprises the following steps:

(a) applying or introducing into/into a product an identification substance blend comprising a paramagnetic phase, or identifying a product comprising an identification substance blend comprising a paramagnetic phase, the identification substance blend having an ESR fingerprint allowing the product to be unambiguously identified,

(b) recording the ESR fingerprint spectrum of the product,

(c) a digital representation of the ESR fingerprint is generated and stored,

(d) measuring the ESR spectrum of the product to be authenticated, and generating a digital representation of the measured ESR spectrum,

(e) the product to be authenticated is verified by comparing the digital representation of the measured ESR spectrum of the product to be authenticated with the digital representation of the stored ESR fingerprint spectrum.

It may be that the digital representation of the ESR fingerprint contains a hash value derived from the ESR fingerprint. For example, information confidential information may be encoded in ESR fingerprint information because the hash value does not allow for the determination of raw data encoded with reasonable computational power; instead, it can be easily verified with knowledge of the raw data (one-way encoding).

The digital representation of the ESR fingerprint assigned to the product can be stored in a blockchain network in an anti-counterfeit and manipulation-proof manner. For example, a distinct non-replaceable token (discrete non-secure token) in the blockchain network may be generated here for each stored digital representation of the ESR fingerprint, so that each different ESR fingerprint may be assigned a different token in the blockchain network, by means of which, for example, transactions (sales, licenses) relating to the product represented by the ESR fingerprint may be digitally imaged and executed.

The verification of the authenticity of a plurality of measured ESR spectra can advantageously be carried out in a common detection step, for example using a zero knowledge proof that enables the calculation (for example the sum of a plurality of individual values) to be authenticated without disclosing the individual values themselves. For example, the authenticity of a plurality of products can be verified in one step, for example by a third party (authority, service provider), without the third party having knowledge of the individual ESR fingerprint spectra and the information encoded with them.

The method steps of measuring the ESR map of a product to be authenticated and the generation of a digital representation of the measured ESR map may advantageously be performed with a mobile terminal device, preferably a smartphone, on which a computer program measuring the ESR map of a product using circuit components of the mobile terminal device, called Software Defined Radio (SDR) circuits, is executed. It is possible here that the ESR pattern of the product is measured using additional permanent magnets or antennas or external switchable circuit components suitable for the purpose. Alternatively, the ESR map may also be measured using the earth's magnetic field.

The invention also relates to a method for verifying the authenticity of a product having an identification substance blend which contains a paramagnetic phase and has an ESR fingerprint which allows a product to be unambiguously identified, comprising the following method steps: the method comprises the steps of recording an ESR pattern of the product with a mobile terminal device, preferably a smartphone, executing on the mobile terminal device a computer program that measures the ESR pattern of the product using circuit components of the mobile terminal device, and comparing the recorded ESR pattern of the product with a stored ESR fingerprint spectrum.

The invention also proposes a device for authenticating a product having an identification substance blend which contains a paramagnetic phase and has an ESR fingerprint allowing the product to be unambiguously identified, wherein the device has: a spectrometer unit arranged to measure an ESR fingerprint, a communication unit arranged to access a database storing digital representations of ESR fingerprint spectra, and a data processing unit arranged to create and compare a digital representation of the measured ESR fingerprint of the product to be authenticated with the digital representations of ESR fingerprint spectra stored in the database.

The authentication device is preferably in the form of a mobile or fixed terminal device, for example a smartphone, on which a computer program for measuring the ESR spectrum of a product using the circuit components of the mobile terminal device can be executed.

The invention finally proposes a computer program product executable on a terminal device, preferably a smartphone, which, when executed on the terminal device, uses circuit components of the terminal device to measure an ESR map of a sample containing a paramagnetic phase.

Drawings

The invention is described in detail below by way of working examples with reference to the accompanying drawings. The figures show:

FIG. 1 is a schematic flow chart diagram of a working example of a method for product authentication in accordance with the present invention;

FIG. 2a ESR spectra recorded at room temperature of powder mixtures of various weight ratios UB and MAG;

FIG. 2b ESR spectra of FIG. 2a versus H_applThe second derivative of (a);

FIG. 3 is a schematic illustration of a measurement arrangement for product authentication in a working example of the present invention;

FIG. 4 is a block diagram of a unit circuit for measuring magnetic resonance spectra;

FIG. 5 contains Fe₃O₄ESR spectra of films of ultramarine blue, MAG and UB layers;

FIG. 6a) Ultramarine Blue (UB), b) phenanthroline (CuCl)₂) C) UB and phenanthroline (CuCl) mixed in a weight ratio of 1:1₂) An ESR spectrum of (a);

FIG. 7 ESR spectra of magnetite at different temperatures;

FIG. 8 ESR spectra of ultramarine blue at 100K and room temperature;

FIG. 9 ESR spectra of ultramarine and magnetite as tablets (a) and suspension tablets (b);

FIG. 10 ESR spectra of various extrudates containing ultramarine blue;

FIG. 11 ESR spectra of various pastes containing ultramarine blue;

FIG. 12 ESR spectra of various pastes containing TEMPO;

FIG. 13 contains TiO₂/SiO₂The ESR spectra of the various pastes of (a); and

FIG. 14 ESR spectra of various pastes containing MgO doping;

FIG. 15 ESR spectra of the compound of example 11 and the mixture.

Detailed Description

The present invention is based on the surprising finding that: ESR spectra are particularly suitable as identification marks for a large number of products, since

(a) ESR fingerprints are generated by the admixture of the product itself or the identification of the product itself rather than by attached or applied labels, bar codes, etc., which significantly improves security against counterfeiting and handling, with detection sensitivity low enough to allow detection in the femtomolar range, and therefore can provide environmentally and functionally unobjectionable markings, which is particularly important in the food and pharmaceutical industries. Surprisingly, even without laborious sample digestion, the sample can be identified therefrom,

(b) the ESR fingerprint can be specifically incorporated into a product by various suitable generation and blending methods, and combinations of methods, and thus can encode desired information,

(c) the reproduction of ESR fingerprints generated by a combination of different production and/or blending methods is extremely difficult without the knowledge of these methods (internal knowledge), which in turn improves the security against forgery, and

(d) ESR maps for product certification can be recorded with relatively low levels of equipment complexity and time requirements.

The flow chart in fig. 1 shows a schematic illustration of individual method steps in a working example of a method for unambiguously identifying and authenticating a product according to the invention.

The product may for example be a pharmaceutical, food or beverage or a precursor or intermediate or a defined constituent thereof, such as a package, blister pack, container, e.g. glass and polymer tubes, syringe, ampoule or reservoir for liquids. The product may alternatively be a textile, textile or leather product, a coin, banknote, security, document, certificate or cheque card or chip card or part thereof, or a gemstone or gemstone semi-gemstone, a medical product, an implant or graft, or a replacement part or supplier part of an industrial product.

In a first method step S1, a blend of identification substances containing a paramagnetic phase is applied/introduced onto or into the product by a suitable method. These methods may include coating, blending, doping, sputtering, chemical radical generation, irradiation (particularly X-ray irradiation), and/or by printing methods. The latter may include letterpress, gravure, porous, screen printing, lithographic printing such as offset printing, digital printing, steel intaglio replication, screen printing, electrophotography (laser printing), powder printing processes such as Xerox and electrospray, electrospinning, precipitation, paper moulding or layering processes, e.g. screen printing, or direct imaging. Suitable starting materials and media for this purpose are, for example, pastes, inks, colorants, gases and vapors, lacquers, stencils, powders, solutions, melts, glasses and their physically active or chemically reactive forms.

In a method step S2, the ESR fingerprint of the product thus processed is recorded and, in a subsequent method step S3, it is converted into a digital representation of the ESR fingerprint by means of fixed rules and then stored in a suitable storage medium, such as a database or a distributed storage medium (distributed ledger), for example a blockchain.

The method steps S1 to S3 are generally carried out under the control of the manufacturer or first distributor of the product in question.

The authentication or verification steps S4-S6 may be performed, for example, by an intermediary, customs authority, end purchaser, user, customer, etc., generally as desired.

In method step S4, the ESR spectrum of the product of the invention to be authenticated is measured and, when it is the original product, the ESR fingerprint of the identification substance blend is detected. In method step S5, the measured ESR spectrum is digitized by a fixed rule and then compared in step S6 with a digital representation of a stored ESR fingerprint spectrum from the manufacturer/supplier in order to thereby verify the authenticity of the product of the present invention.

The invention can be made available, for example, by pharmaceutical companies, manufacturers, suppliers and experts along the value creation chain to the end customer, such as the patient or the collector or the end owner.

The following sections set forth various aspects of the invention in detail.

ESR spectra

Systems with gyromagnetic properties are known in which the charged electrons exhibit spontaneous magnetic ordering. These are distinguished from those systems in which magnetic ordering is caused by localized electron spins. The latter are important in chemically complex atoms, especially almost all coloured minerals, usually as technical fillers and pigments or rare earths. Other important paramagnetic centers are insulators such as synthetic and natural polymers, and organic dyes such as quinones, anthocyans and polyphenols.

However, as the atomic number of a chemical element, which is the central part of an atom corresponding to localized electron spins, increases, the magnetic moment of the localized electron spins are more and more affected by the spin-orbit coupling effect in the main group and transition group. Materials scientists are therefore also aware of micro and macro spin lattice systems up to and including metallic conductors.

If the mentioned systems, i.e. ion-atom, chemical complex, insulator radicals such as polymers, mineral inert or natural minerals, semimetal or metal systems, are irradiated with microwaves, different steady-state or dynamic electron spin resonance or ESR spectra are obtained in the most general sense.

In principle, systems with only unpaired electrons are suitable for ESR spectroscopy, such as free radical systems, paramagnetic transition metals, bar magnets and semiconductors. The paper by Chem.Ing.Tech.2014,86,11, page 1871-1882 of Angelika Bruckner indicates that, depending on the system, the resonant electron spins may undergo complex interactions, for example between electron spins and nuclear spins, and/or be influenced by three-dimensional symmetry. In the measurement of systems consisting of a plurality of superimposed components, this leads to complex ESR spectra which are often not easily interpretable. While this demonstrates the high potential of spectroscopy for studying unpaired electron systems, it can be seen at the same time that the combination of different systems cannot be easily assigned to a linear or easily calculated combination of ESR spectra.

For example, if a given substance is monitored on its way through the human or animal body, conclusions can be drawn about the physical and/or chemical transformation of the aggregate or substance by detecting the change in site, identity and ESR spectra over time, for example during their dissolution in the digestive process or in other metabolic processes.

Dorfman, j.exp.theor.phys.48(1965),715 evaluated how macroscopic magnetic observables in such systems were fundamentally dependent on grain size. In summary, in the materials concerned here, in particular in medical-technical preparations, the behavior of the spin system, the probe giving the total aggregate of magnetic moments, and the usability of legal regulations can be difficult to predict.

The intensity of the ESR signal, which is equivalent to the integral of the absorption signal, and the spontaneous magnetization M of the sample_sProportional to the ratio, as described in papers by Advances in Physics 42(1993),523, by B.Heinrich and J.F.Cochran. The line width of the ESR signal follows a dependence of the form:

ΔH～K₁/M_s

wherein K₁Is the magnetocrystalline anisotropy constant; see ya.g. dorfman, j.exp.theor.phys.48(1965), 715.

The magnetic shape anisotropy also has a significant effect on the shape and position of the ESR signal. The magnetocrystalline anisotropy constant of the known ferromagnetic or ferrimagnetic material is 103-106J/m³Thus, the ESR line width was observed:

ΔH～(10²…10⁴) OeV.K.Sharma and F.Waldner, J.appl.Phys.48(1977), 4298A ferrimagnetic Fe of 1000Oe was observed at room temperature₃O₄Line width Δ H in the powder. It should be noted that the magnetocrystalline anisotropy constant of magnetite is about 3 x 10⁴J/m³。

It is also known that in particles equal to or below the critical size, above the critical temperature (also called the blocking temperature), thermal fluctuations dominate the magnetocrystalline anisotropy, and therefore such particles show superparamagnetic behavior. In contrast, below the blocking temperature, the particles have ferromagnetic or ferrimagnetic behavior. The critical dimension of the particles is determined by the magnetocrystalline anisotropy. In magnetite, the critical particle size is about 14 nm; see G.Vallejo-Fernandez et al, J.Phys.D: appl.Phys.46(2013), 312001. Magnetite nanoparticles having a particle size of 14nm or less can have relatively narrow ESR lines which are characteristic paramagnetic and superparamagnetic particles, as discussed in papers of j.salado et al, j.non-crystalloid Solids 354(2008),5207 and r.berger, j.magn.magn.mater.234(2001), 535.

A particular form of such measurements is to detect the effect of paramagnetism on imaging nuclear spin tomography, but their measurements are based on much weaker nuclear spin interactions.

FIG. 1a shows by way of example magnetite Fe₃O₄ESR spectra of various mixtures of powder (MAG) and Ultramarine Blue (UB).

MAG ═ 30:1, weight-based mixing ratio, g ═ 2.026S₃The ESR signal of the radicals is still apparent. It can be concluded therefrom that all S of UB₃The radicals have not entered into a strong magnetic dipole interaction with the MAG. But even at elevated MAG content, corresponding to a mix weight ratio of UB: MAG 30:3, a significantly broader ESR signal is obtained at g ═ 2.307, which is attributed to the ferrimagnetic MAG particles. In contrast, S₃The signal of the free radicals is still hardly apparent due to MAG and S₃Stronger magnetic interaction between free radicals. This effect is further enhanced where the weight ratio of MAG is increased to a UB: MAG-30: 4 ratio.

FIG. 1b shows these line shapes versus the external magnetic field H used for spectroscopy_applThe second derivative of (a). Especially at a UB: MAG ratio of 30:4, the quadratic differential line shape shows the radical signal here even more clearly.

The effect of the magnetic interaction between MAG and UB as the MAG content increases is perceptible in the corresponding peak-to-peak distance that is linear with respect to the second derivative of the magnetic field.

Specific generation of characteristic ESR spectra

One aspect of the invention relates to the selective generation of specific characteristic properties of ESR spectra, such as resonance frequency or line width, which can then be used for the encoding of information (product characteristics, manufacturing site, manufacturing time, intended use, rights, etc.).

The present invention includes various combinations of algorithms, data architectures, and known or future recording and tracking systems. The identification substance blend may be applied throughout the production chain and at all stages of production.

Surprisingly, the essential properties of a particular stable atomic magnetic property with a sufficiently large magnetic moment are in the range of the necessary physical resolution and sensitivity, which is not altered by the conventional production conditions, and which can be adopted and handled from raw materials up to downstream transport and distribution in the value creation chain. Very surprisingly, suitable components (e.g. dopants) of the identification substance blends according to the invention for most applications can be present in the list of inactive pharmaceutical ingredients and also in the defined environmentally friendly pigments and functional substrates and coatings for many industries, for example polymeric minerals with minor lattice anomalies and impurities, such as silicates or salts and oxides.

The identification substance blend may be a paramagnetic coating, or a filler component of the paramagnetic mineral, glassy, paramagnetic molecule or paramagnetic ion salt type in a polymer matrix or binder matrix, and a phase in which paramagnetic centers may be continuously generated, for example by ionizing radiation or chemical reactions, for example by layer-by-layer processes. The readout magnetic field is directed at the electron paramagnetic center by a variable or steady magnetic field that penetrates the body and generates an energy level that can be repeatedly read out by means of the high frequency cell of the ESR spectrometer. The resonance signals here can be additive lines, or they interact (couple) with one another in particular and in particular according to a combination characteristic, which considerably extends the diversity of the types of markers, marker variants.

Other physical magneton interactions may be generated by ionization, for example by means of ionizing radiation. The Kim et al publication-Electron Spin Resonance Shift and Linear width of Nitrogen-Vacancy Centers in Diamond a Function of Electron Irradation Dose "describes, for example, the controlled Shift in the ESR Resonance frequency and the increase in line width in the case of Diamond samples bombarded by electrons.

The polymer matrix can be used to effectively provide ESR fingerprint for a single fabric. The ESR signal is well randomized in order to obtain good bit combining. The signal is not altered by the influence of industrial formulations, preparations or production processes extending to the melting of polymers and glasses. The layer-by-layer miscibility of the identification substance blends containing paramagnetic phases enables virtually unlimited use on or in textiles, leather, textile materials or paints of polymer powders up to and including glass processes, extrusion or additive manufacturing processes (3D printing).

Measurement of ESR spectra

One advantage of the present invention is that ESR spectra can now be measured with a relatively low level of equipment complexity and time requirements. More particularly, the signal-to-noise ratio is much better than in the case of nuclear spin resonance measurements (NMR) known from medical diagnostics.

The disclosures of w.tang and w.wang, meas.sci.technol.22(2011),1-8 describe NMR spectrometers housed on a unit circuit with software-defined functionality (— single board software-defined radio (SDR) spectrometers "). The circuit arrangement provided in this article is shown in fig. 3. The SDR-based architecture, implemented by a combination of a single-chip Field Programmable Gate Array (FPGA) and a Digital Signal Processor (DSP) with RF front-end circuitry, makes the spectrometer compact and reconfigurable. The DSP acts as a pulse programmer, communicates with a personal computer via a USB interface, and controls the FPGA via a parallel port. The FPGA performs digital processing steps, such as a Numerical Controlled Oscillator (NCO), a Digital Downstream Converter (DDC) and a gradient waveform generator. An NCO with flexible control of phase, frequency and amplitude is part of a direct digital synthesizer for generating RF pulses. The DDC implements quadrature demodulation, multi-stage low-pass filtering, and amplification conditioning to generate a bandpass signal (receiver bandwidth from 3.9kHz to 10 MHz). The gradient waveform generator is capable of emitting a pulsed wave shaped as a gradient and assisting eddy current compensation. The spectrometer detects the NMR signal directly to 30MHz in the baseband scan and is suitable for low field (<0.7T) applications.

Since ESR signals have a much better signal-to-noise ratio than NMR signals, readout of the ESR spectrum is of course possible with lower equipment complexity, especially with mobile terminal devices such as smart phones, by installing a suitable software application (software defined radio SDR) making use of the electronic components already present in the device.

Fig. 3 shows a working example of such a device according to the invention for authenticating a product according to the invention in a schematic view. The SDR software application has been loaded onto a mobile terminal device 10 which uses a magnet or magnetisable member 30 to detect the ESR map of the identification substance blend 20 of the product according to the invention. The identification substance blend 20 may be a paramagnetic coating 21, or a filler component of the paramagnetic mineral, glassy, paramagnetic molecule or paramagnetic ion salt type in a polymer matrix or binder matrix 22, or a phase 23 in which paramagnetic centers are generated, for example by ionizing radiation or chemical reaction. The magnetic or magnetizable member 30 is aligned to the electron-paramagnetic center by a variable or stable magnetic field H that penetrates the body (vertical arrow) and generates an energy level that can be repeatedly read by means of the high frequency cell of the ESR spectrometer or the SDR configuration in the mobile terminal device 10. The resonance signals here can be additive lines, or they interact (couple) with one another in particular and in particular according to a combination characteristic, which considerably extends the diversity of the types of markers, marker variants. The component 30 generating the magnetic field H may itself be housed in the terminal device 10 or be part of the environment in which the situation is measured (e.g. the earth's magnetic field).

Field scanning and fixed field devices can now be easily miniaturized. The pulse height (energy) is here predefined by the H-field. Which can be generated and changed in an energy-saving manner by permanent magnets or excitation coils. The pulse sequence portions may also be superimposed therein. Separate high frequency transmitter and receiver coils may also transmit the pulse and receive the FID components. The geometry of the tuner can be miniaturized and is determined by the surface of the object or paramagnetic marker according to the invention.

The above publications by Tang and Wang give a detailed description of such a measuring device for NMR nuclear spins: a method comparable to ESR in terms of physical/quantum mechanics, but in which the spin-magnetic moment is measured several orders of magnitude lower.

Due to the use of a direct signal synthesizer architecture, the necessary analog-to-digital converters and power drivers, as well as the entire high frequency electronic system, are kept at a particularly low noise level, where a single-chip Field Programmable Gate Array (FPGA) chip constitutes a programmable-software defined radio "(SDR) in the immediate vicinity of the multiplexer of the smaller high frequency coil. Thus, there is virtually no noise component resulting from the mixing and filtering of analog signals by digital mathematics.

However, a practical surprise and revolution in the smartphone industry is that an analog-to-digital converter with as wide a programming latitude as possible and even an FPGA chip such as the ICE5LP4K chip in iPhone 7 enable simulation of an SDR in real time or with a connection to a network in a system according to the invention, with database access and global connectivity. Even now, in these field devices, a number of components are available to digitally record the necessary pulses, dc control and HF-FID acquisition, to filter them mathematically-digitally and to process them.

This means that even before a specific hardware adaptation, for example by means of a specific-ASIC "component (custom designed chip), the SDR concept of modern smart phones is able to use existing drivers and-DSP" (digital signal processing) chips to allow the programmable ESR reading apparatus for authentication according to the present invention to have a minimum of peripherals (e.g. permanent magnets, shields, high frequency coils, field coils, power drivers) by installing an application (usage program).

Block chain network

In the same way that the internet revolutionized the disclosure, storage, and dissemination of information, blockchain technology is in the process of revolutionizing the storage and transfer of values such as money, corporate stocks, and the like. The block chain network consists of a plurality of interconnected network nodes, the common state of which is updated in a decentralized manner by means of a consistency (consensus) protocol and stored in a cryptographic form in a chain of interconnected blocks (— block chain "). As in the case of bitcoins, the agreement protocol deciding the content of a block may be based on a so-called workload proof protocol, where multiple-miners "compete to solve the cryptographic problem (generate hash values smaller than a certain threshold) in order to generate the next block and win the associated prize (in 2019: 12.5 bitcoins). In order to participate in the next round of contention, the network node must first confirm the validity of the current block, which establishes consistency with respect to the network state. As an alternative to workload attestation protocols, there are also equity attestation protocols in which the consistency with respect to the network state is achieved not by using (power consumption consuming) computational power but by depositing value carrying network tokens by means of probabilistic design methods. Furthermore, there are mixed-form and closed (private) blockchain networks, where authorized network nodes decide on the network state. In particular, public blockchain networks based on workload-proof consistency protocols are characterized by a high degree of operational security, since the modification of past events would require the reconstruction of the entire middle-history "of the blockchain by extremely computationally intensive redo of the consensus mechanism. There is also a high security against data loss due to the decentralized storage of network states in a plurality of network nodes (-distributed ledger); there is no single point of failure.

In a blockchain network, tangible goods (products, outlets, replacement parts, raw materials, pharmaceuticals, and non-pharmaceutical products) and intangible goods, such as information, monetary funds, or commercial shares, may be represented and traded. Due to the public network state, which is transparent to all, the contracting party's risk of default (-counterparty risk) is reduced, the degree of trust of counterparties required for transaction execution is reduced and replaced by trust in the mathematical and game theory consensus algorithms.

In cooling chains, for example, in the event of physical changes in location (warehouse, sales department, customer) or transactions (e.g., ownership changes), various different types of such blockchain networks are now being used to track and store information about goods. Ideally, the single origin of the single unit, package, packet of packages returns to the source of the final product and even seamless traceability through its precursor, paste, premix and raw material sources is possible.

If these data are stored in encrypted form, for example in the form of hash values, in the blockchain, the network can also be a secure storage site for secretly-or for example randomly-generated product knowledge. The authenticity of the data may be verified by comparing the time-stamped hash value stored in the blockchain with a hash value generated from the private confidential data.

Product packaging to date is a significant weakness in order to compare the reality stored in a blockchain network with the physical reality of a manufactured or processed product. Smart tags, such as RFID, must be attached to and removed from individual products, which requires a housing and a securing mechanism. This problem is solved by an identification substance blend according to the invention comprising a paramagnetic phase having a well-defined product identification ESR fingerprint independent of product packaging or the like. Like the entries (entries) in the blockchain ledger, the fingerprint ESR can only be changed particularly with great difficulty. Thus, the present invention constitutes an explicit and manipulation-proof ledger for products in the physical world as a counterpart to the distributed manipulation-proof ledger provided by the blockchain network.

Observation of chemical conversion Processes

The product according to the invention may be configured as a subject, for example for ingestion in the human or animal body.

The inventors have completely surprisingly found a further correlation. Although in the state of the art ESR spectra are considered as typical characteristics of the irradiated substance, it is possible, for example, to solve the technical problem of how to systematically control and anticipate the transformation process of the substance, in particular by providing the characteristic ESR spectra for the respective compositions through the combination of various systems, for example in the form of mixtures, compounds or, in general, compositions consisting of various macroscopic or microscopic phases. Compositions consisting of at least two materials have been found, wherein at least one material in pure form other than the composition can give a characteristic ESR spectrum. However, in compositions with at least one additional material, the ESR spectrum in particular surprisingly decays significantly or disappears completely. In this case, a subject having multiple phases and being ingested by or within a human or animal body has at least two phases with different electron spin resonance spectra. At least one of the phases has gyromagnetic or localized magnetic properties. The ESR spectrum of rare earths is found to be less inhibited too much and, depending on the combination, the host displays a decay of the ESR spectrum or a superposition of different ESR spectra.

It may be advantageous when at least one phase of the body according to the invention has a purely paramagnetic center, preferably an S radical, preferably selected from ultramarine. It may be particularly advantageous to select superparamagnetic particles in addition to non-ultramarine, which superparamagnetic particles preferably comprise or consist of: magnetite or maghemite or pyrite or iron containing compounds such as amethyst. In the case of such particles, a similar ESR signal was found.

Preferably, at least one phase of the body according to the invention has at least an overall ordered state which may be ferromagnetic, ferrimagnetic and/or antiferromagnetic. More preferably, the phase comprises iron-oxygen compounds. Most preferably, at least one phase is magnetite or a phase consisting of the Fe-O system. The phases mentioned are in particular substances which are harmless to the human or animal body. Furthermore, such selected phases may be pronounced in the form of a tablet formulation. Surprisingly, the magnitude of the effect of attenuating or suppressing the ESR spectrum.

These phases can also be reprocessed in particle dispersions. It is also surprising that pharmaceutical preparations can therefore be provided in a simple manner, since in particular magnetite or materials having an Fe — O phase have very good compatibility with the human body and are extremely safe even when used in human medicine. Since the body does not comprise any highly toxic substances or harmful free radicals, the body can be used equally reliably in the gastrointestinal region.

In any spectroscopy, the better the signal-to-noise ratio of the system considered, in this case the body considered and the subject according to the invention and the instrument for detecting ESR spectra, the better the measurement results achieved. Human and animal organisms have so far mainly shown diamagnetic behavior in magnetic fields and the diamagnetic background hardly collapses (distpt), even more sensitive nuclear spin tomography. Thus, when using a body according to the invention, only very low magnetic field strengths are required to measure the ESR spectrum.

Furthermore, it may be advantageous if, in the body according to the invention, at least one phase is encapsulated by at least one further phase. More preferably, one phase acts as a membrane to encapsulate the other phase. Preferably, the thickness of the film and phase may be selected such that the ESR pattern of the inner encapsulated phase is completely obscured by the ESR pattern of the outer encapsulated phase.

If the passage of the body through the human or animal body according to the invention is associated with a decomposition of the body, the ESR signal of the encapsulated phase appears more strongly with the decomposition of the encapsulated phase in a time-dependent manner. This simple time dependence is another advantageous property of the body.

If magnetite particles are selected in at least one phase of the host, the inventors believe, without being bound to a particular theory, that the ESR pattern may be caused not only by intrinsic magnetic properties, but also by dipolar interactions between the magnetite particles. The interaction is preferably influenced by the shape of the particles, e.g. spherical, needle-shaped, cubic, and in general by the spatial distribution of the magnetite, e.g. a film. These forms show different demagnetizing fields (demating fields).

The more ferrimagnetic or ferromagnetic components the body according to the invention has, the more strongly the ESR signal is attenuated. In this context, absorption of microwaves emitted in the spectrum is suspected.

It is also possible to envisage bodies in which the ferromagnetic phase and the radical phase, such as the ultramarine phase, are present in spatially separated form, preferably in the form of spatially separated aggregates. This corresponds to different ESR spectra. If the body is subsequently disintegrated, there is a temporary mixing of the two phases and, given a suitable ratio of one phase to the other, the ESR pattern of one phase, preferably of ultramarine, will temporarily disappear completely. Thus, the decomposition of the body in the body can be specifically assigned to the decomposition process.

It may also be advantageous when the body according to the invention has at least three phases, wherein one phase is preferably paramagnetic, preferably selected from (phenanthroline) CuCl₂. In this case, the shape of the ESR wire is more complex and in the decomposition of the mixture of the phases, for exampleTime-resolved behavior was obtained as on the breakdown of subjects during the metabolic processes of the body, demonstrated by the time dependence of the ESR map. Progressive decomposition may be recorded.

Thus, preferably the magnetic, paramagnetic and free radical phases may be combined. If the body of such a composition decomposes in the body, with the loss of correlation of the decomposition of the magnetic phase or its detachment from the body, another-eventually "ESR wire shape appears, which is clearly different from the ESR wire shape of the non-decomposed body according to the present invention.

Such a breakdown process is advantageous in the case of non-therapeutic procedures, for example within the scope of non-medically motivated nutritional or nutritional habit problems of an individual.

However, the disintegration process is also the target of medical implants, for example in their functional coating, in particular in the oral form of nutritional, dietetic or therapeutic preparations, for example in capsules, tablets, films and granules and multiparticulate administration forms in food technology and pharmaceutical technology independently thereof. They can be very specifically designed via the choice of the excipients used, for example the capsule shell, the granule coating and the medical-technical materials used, and are therefore controlled via the formulation process. The present application preferably gives solubility using such adjuvants and excipients, more preferably pH and time dependent solubility. In the case of medical-technical implants, hydrolysis in particular leads to the desired absorption of the matrix and the coating. Examples include approved materials for surgical materials, and polymers

Methacrylic acid esters and

polyesters, modified starches such AS HMPC, HMPC-AS or polylactate (polylactate) and co-glycolic acid (co-glycolic acid) or co-polycaprolactone, and absorbable medical technology coatings or implants. Here, such insulator polymers, in particular medical-technical polymers, may themselves carry paramagnetic centers, as for example in the case of polymers with the aid of electron beams or gamma raysRadiation sterilization by radiation. It is therefore also preferred that the body according to the invention has at least one phase with at least one medically technical polymer with paramagnetic centers, preferably isolated free radicals.

Thus, the appearance of the final ESR line shape can be considered as a fingerprint of the subject during disintegration in the body. This is illustrated in detail in example 2 and fig. 6.

Since the mixed phase is thus distinguishable from the clean phase and the decomposition of at least one phase of the body according to the invention is detectable, it is also possible to detect the dose in the body, which means a mixture of differently structured bodies in the body.

Working examples of the invention therefore also provide the use of a body according to the invention, preferably having at least three phases, for monitoring decomposition processes in the human or animal body.

Detailed Description

Examples

The present invention is illustrated in detail below by examples.

In the context of the present invention, the term-room temperature "is understood to mean an ambient temperature of about 20 ℃.

Example 1:

the loose powder premix allows simple change to a well-identified substance blend during the production process for individual tablets or small parts (which can only be realized with difficulty by other methods), microelectronic components or physical labels.

The ingredients of such powder premixes may be:

1) microcrystalline cellulose or HPMC

2) Vestamid or PVP

3)PEEK

4)Eudragit

5)PLA

Numbering	Standard substance	Paramagnetic center
				1	Cu/Al₂O₃	Cu (II) alone
2	Mn/MgO	Mn (II) alone
			3	TiO₂Or ZrO₂	F center
4	C₃N₄	Conduction band electronic signal
			5	Ultramarine blue	S₃ ^-

The following variants are conceivable here:

a) all mixed oxides are diluted with adjuvant 1

b) The oxide mixture of the pigments without the two strongest signals is diluted with auxiliary 1

c) a compacts (e.g. from IR briquetting presses)

d) b but diluted with adjuvant 2

e) Irradiated adjuvant 3 (control)

f) Irradiated adjuvant 4 (control)

g) Irradiated adjuvant 5 (control)

h) b, dilution with

auxiliaries

3, 4 or 5 (according to the success) and irradiation

i) b, dilution with

auxiliaries

3, 4 or 5 (according to the success) and no irradiation

j) All oxides mixed in

auxiliaries

3, 4 or 5 (according to success), cf. h and i

k) If a is further diluted with auxiliary 1 (so diluted that it is still only detectable, e.g. 1:100)

l) if the auxiliary 3, 4 or 5 in irradiated form is active, two of these are mixed with the two oxides in the corresponding dilutions

m) a water-moist paste of one of the above mixtures

n) melting the mixture (in cooled form, available with ultramarine blue)

In the case of use as a laminate or extrudate, regulatory aspects with respect to the maximum concentration of a particular substance may be considered.

Example 2: inventive body comprising ultramarine blue and magnetite

Mixing magnetite Fe₃O₄Powders (abbreviated as MAG in the context of the present invention, under the trade name of Cathay pure Black B2310, available from Cathay Industries) and ultramarine blue powders (abbreviated as UB or ultramarine, under the trade name Kremer Pigment, product number 45000) were mixed with the aid of a pestle using a mortar in the weight ratio MAG: UB of 1:30, 3:30 and 4: 30.

The ESR spectrum of the mixture thus obtained is recorded in the X-band (9.5GHz) at room temperature and under 6.3mW of microwave energy, at a modulation frequency of 100kHz and an amplitude of up to 5 Gauss.

Furthermore, in the case of an additional dilution of the concentration of MAG with methylcellulose or UB, a thin layer containing MAG was applied in each case to a different adhesive tape, wherein each of these components was provided beforehand in the form of a suspension in ethanol. The ESR spectrum of the layer thus obtained was recorded.

To ensure that UB and MAG have been brought into intimate contact with S₃The interaction of the free radicals is sufficiently large, first to noteThe ESR spectra were recorded on separate thin layers. Subsequently, in each case, an ESR spectrum was recorded on the adhesive tapes bonded to one another.

FIG. 2a shows ESR spectra of various mixtures of MAG and UB.

MAG ═ 30:1, weight-based mixing ratio, g ═ 2.026S₃The ESR signal of the free radical is still readily visible. It can be concluded therefrom that all S of UB₃The radicals have not entered into a strong magnetic dipole interaction with the MAG. However, even with an increased MAG content, i.e. corresponding to a mixing weight ratio of UB: MAG of 30:3, a clearly broader ESR signal is obtained at g of 2.307, which is attributed to the ferrimagnetic MAG particles. In contrast, S₃The signal of the free radicals is still hardly apparent due to MAG and S₃Stronger magnetic interaction between free radicals. This effect is further enhanced where the weight ratio of MAG is increased to a ratio UB: MAG of 30: 4.

These line shapes correspond to the external magnetic field H used for spectroscopy_applIs shown by the schematic in fig. 2 b. Especially at a UB: MAG ratio of 30:4, the quadratic differential line shape shows the radical signal here even more clearly.

The effect of the magnetic interaction between MAG and UB as the MAG content increases is perceptible in the respective peak-to-peak distances that are linear with respect to the second derivative of the magnetic field.

FIG. 5 shows the ESR spectra obtained on thin layers of UB and MAG on the adhesive tape.

As expected, the ESR signal for the layer containing MAG and containing UB corresponds to the ESR signal for the pure MAG and UB components.

However, if a tight bond is provided by the adhesive strips adhering to each other, a different ESR signal is obtained.

Found by S₃The free radical induced ESR signal decays in intensity, whereas MAG's ESR signal loses little if any intensity, but undergoes a slight shift from a value of g-2.766 to g-2.897.

Assuming that this effect is attributable to the magnetic dipole interaction between MAG and UB, this may mean that even a thin layer is on the adhesive tapeAll of which affect S simultaneously₃ESR signal of free radicals and ferromagnetic ESR signal.

The ESR spectra just illustrated show that in a mixture of UB and MAG, even a proportion of MAG of about 10% by weight is sufficient to convert S to₃The ESR signal of the free radicals is suppressed below the detection limit. Even contact of thin layers containing both components attenuates the signal to about half of the value.

In contrast, if only the paramagnetic component is mixed with the UB, a nearly invariant form of S is obtained even when the ratio of paramagnetic component is much higher than MAG₃Free radical ESR signal.

Without being bound by a particular theory, the inventors suspect that the cause of ESR signal migration in fig. 5 is due to the magnetic state of the particles causing natural demagnetization. The resulting internal field H_intCan be approximated by a simple relationship:

H_int＝H_appl–N M，

where M is the magnetization, N is the demagnetization factor, H_applIs an external magnetic field used for spectroscopy. Demagnetization depends on the geometry of the M-containing particles or substances, and the overall form of the body composed of such particles or substances. In the form of a layer, for example leading to the spectrum of fig. 5, a much stronger demagnetizing field is found than that produced by spherical or cubic particles or bodies when an external magnetic field is applied at right angles to the layer surface. Here N can be assumed to be close to 1.

In the case of spherical or cubic particles or bodies, in particular, which are not in the layer arrangement, N can be set to ≈ 1/3. It is also suspected that when layers containing magnetite and ultramarine are stacked one on top of the other, the demagnetizing field causes a shift in ESR spectrum as a result of the change in magnetostatic interaction, as compared to the above-described dipolar interaction in the case where magnetite and ultramarine are mixed together.

Example 3: containing phenanthroline (CuCl)₂) And ultramarine blue

As example 2, except that the mixture, and not MAG, was treated with paramagnetic dichloro (1, 10-phenanthroline) Cu in a 1:1 weight ratio^II(phenanthroline (CuCl)₂) ) complexes andultramarine blue is provided.

Albeit due to MAG and ultramarine blue S₃ ^-Considerable attenuation effect was observed in example 2 due to strong magnetic interaction between radical anions, but paramagnetic component and Cu^IIIon (d)⁹ Spino 1/2), namely phenanthroline (CuCl)₂) This interaction does not exist between the complexes.

Paramagnetic phenanthroline (CuCl)₂) The ESR spectrum of the complex showed Cu at g 2.246 and g 2.061^IIAs shown by line shape b) of fig. 6. Mixture with UB gives an ESR spectrum as Cu^IIAnd S₃ ^-Superposition of free radicals (fig. 6, line shape c)). The line shape c) corresponds to a clearly very good approximation to the direct sum of the line shapes a) and b); see line shape a) + b of fig. 6). This is shown in Cu^IIS with ultramarine blue₃ ^-The magnetic interaction between them disappears.

Example 4: body according to the invention as a tablet suspended in water

By adding 10mg of Fe₃O₄A mixture of 10mg of ultramarine blue and 130mg of methylcellulose was subjected to a pressure of 10 bar for 2 minutes and the mixture was compressed into tablets. The thus obtained tablets were pulverized and suspended in water in a beaker. For ESR measurements, samples of the suspension were introduced into the glass capillary after different times. Different ESR spectra were obtained as a function of time, which are shown in fig. 9, in particular the line shape (a) of the not yet suspended tablet, the line shape (b) of the signal of the previously suspended tablet.

The apparent total intensity of the ESR signal shows the suspended solids content to change over time. Thus, for a simple dissolution of the body according to the invention, a monitoring of the disintegration process of the invention is also possible. Line shape (c) in fig. 9 shows ESR signal without magnetite for comparison.

Comparative example: ESR measurement of pure magnetite or ultramarine

ESR spectra in the band were recorded at different temperatures on a solid sample (each magnetite under the trade name of-Cathey Pure Black B2310(40969) ") and an ultramarine sample (the trade name of-Kremer Pigment (45000)").

Pure magnetite exhibits a typical broad asymmetric singlet state of ferromagnetic behavior, with its line shape reversibly changing with increasing temperature, as shown in fig. 7. Such behavior may be due to the superposition of ferromagnetic domains of different structures and/or orientations.

ESR spectrum of ultramarine blue contains S₃Narrow isotropic signal of free radicals; see fig. 8. Typical temperature behavior is observed for purely paramagnetic centers, i.e. the intensity increases with decreasing temperature.

Example 5: extrudates of the invention comprising ultramarine blue

Various extrudates containing ultramarine blue were prepared and the ESR spectrum was measured. Fig. 10 shows the spectra of different extrudate samples, measured at 20 ℃, normalized to the same sample mass of 50 mg. Extrudate 2 showed a weak signal at about 3400G, which may be attributed to Cu²⁺Species, i.e. Cu²⁺Typical hyperfine structures of (a) are not visible. The source of the weak signal at about 3600G in

extrudates

1 and 2 is unclear. This may be due to paramagnetic defects. Extrudates 3 and 4 show a strong ESR signal for ultramarine blue.

Example 6: paste of the invention comprising ultramarine blue

FIG. 11 shows the ESR spectra of three different paste samples, each 50mg, measured at 20 ℃.

Pastes

5A and 5B showed ESR signals of ultramarine blue, and paste 5C showed Cu²⁺Of the signal of (1).

Example 7: TEMPO-containing pastes of the invention

FIG. 12 shows ESR spectra of various paste samples (50 mg each) mixed with 0.02mg of 2,2,6,6, 6-tetramethyl-1-piperidinyloxy (TEMPO radical) measured at 20 ℃. A) A TEMPO signal; B) ultramarine blue signal (pastes 5B and 5C), and Cu²⁺Signal (paste 5C). Samples were prepared by mixing the individual pastes with a solution of TEMPO in acetone; the ESR spectrum was measured after evaporation of acetone (100. mu.l).

Example 8: containing TiO₂/SiO₂The paste of the present invention

FIG. 13 shows TiO in a mixture of 20mg measured at 20 ℃₂/SiO₂Various kinds ofESR spectra of paste samples (50 mg each). By contacting a single paste with solid TiO₂/SiO₂The samples were prepared by mixing.

Example 9: pastes according to the invention comprising doped MgO

FIG. 14 shows MgO (Mn in MgO) mixed with 10mg of Mn (II) contaminants measured at 20 ℃<1%) of the various paste samples (40 mg each). A) Mn separated in MgO matrix²⁺The ESR signal of the ion; B) the ESR spectrum of (A), but with different X and Y axis ranges, in order to show a slightly masked EPR signal of ultramarine. For comparison, the ESR spectra of pastes C and B are incorporated into the figure.

For the following examples 10 to 12, ESR measurements of the following labeled samples and labeling mixtures were performed as follows, with no objection to the technical-related function and approval-related toxicity and environmental relevance:

the sample used for ESR measurement may be analyzed as a solid or a liquid. For solid materials, fused silica sample tubes were used, corresponding to sample sizes of about 10-1000mg (depending on the sample tube diameter). For liquid samples, a volume of about 50 μ l was used, drawn through a glass capillary. The glass capillary was then inserted into a fused silica sample tube for measurement. Before measuring the sample, the instrument underwent a heating cycle, which took 15 minutes and reached a final temperature of about 31 ℃. The temperature range during the measurement was 31. + -. 2 ℃. The sample tube is then introduced into the measuring cell (ideally, the central part of the sample (half the height of the sample in the sample tube) is 62mm from the sample holder surrounding the sample tube at the upper end). The scan time was measured for 60 seconds in the magnetic field range of 0 to 400mT under modulation of 0.2mT and 10mW microwave power. After the measurement, the ESR spectrum was analyzed for possible characteristic peaks. These peaks are characterized by their position in the magnetic field, their strength (intensity/height), their width, their area, their individual appearance, and via their distance from each other in the event that multiple peaks are detected. The position in this case is usually reported as the magnetic flux density (B) in millivolts tesla or dimensionless as a factor called the g-factor. ESR measurements were performed using an MS 5000(11-0185) instrument from Freiberg Instruments GmbH (Freiberg, Germany). For simplicity, the samples measured were divided into: (+) -no signal with pre-excitation, (+) -signal excited by X-ray, and (-) -no signal.

The compounds/mixtures used and measured were:

copper (II) (++) sulfate natural signal, stable in most substrates

Manganese (II) chloride (++), as before, but with more redox changes, functional

Manganese (IV) oxide (++), a coupled signal with very good characteristics, functionality

Zirconium (IV) oxide (++)/(+), weak natural signal, activatable by hard X-ray irradiation

Lactose monohydrate (++)/(+), quantitatively activatable by X-ray irradiation, slight natural signal component

HPMC (-), No Signal, No activation by X-ray radiation

HPMCAS (-), matrix, no signal, not activatable by X-ray irradiation

Titanium dioxide (++), naturally more pronounced

PVP (Kollidon 30) (-), No matrix Signal

·

E, L, RL, FL 30D (+), signals after X-ray irradiation, show typical signal saturation, are nonlinear according to dose

Natural ultramarine blue (++), strong significant signal, extremely robust, all pigment modifications and particle sizes

D (-) -mannitol (+) signal after X-ray irradiation, showing dose linearity

Diamond powders (++), which, depending on the local doping of the formation, exhibit high local resolution in the crystal lattice

Magnesium oxide (++), signal, pigment

Ink black (carbon black and additives) (+ +)/(+), signal after X-ray irradiation, weak baseline signal, functionality

Print paper, white, primed with titanium dioxide as the pigment signal (+ +)

Printing paper (++) with local ultramarine doping, signal superimposed to the primary excitation signal

D (+) trehalose (+), Signal after X-ray irradiation

Microcrystalline cellulose (MCC; Avicel PH) (+), signal after X-ray irradiation

Polylactide-co-glycolides

(+), post-X-ray irradiation signal

Protein (triple helix collagen) (+), characteristic signal after X-ray irradiation

A mixture of lactose monohydrate, MCC, natural ultramarine blue, diamond powder, copper (II) sulfate and magnesium oxide (coded blend).

Example 10

The above encoded blends were measured initially and subsequently diluted. In this case, a mixture was prepared from equivalent masses of natural ultramarine blue, diamond powder, copper (II) sulfate and magnesium oxide. Lactose monohydrate and MCC (the equivalent mass of lactose monohydrate and MCC to each other) are then added to the mixture. For the initial encoding blend, the mixture was used at 2/3:1/3 parts by weight relative to lactose monohydrate + MCC. Then, encoded blends with higher proportions of lactose monohydrate + MCC were produced, with the mixtures diluted to the initial concentrations of 1/2, 1/4, and 1/8.

The spectral curves show an additive signal effect over the entire magnetic field range of the scan, with a maximum intensity of 4.5% (mass/mass) diluted to 2.25%, 1.125%, as low as 0.5625% matrix dilution, and a minimum intensity curve of about 10 relative intensity units as noise margin, which is still much higher than the signal-to-noise ratio when using this method. Surprisingly, without special purity requirements of the laboratory and the substance, mixtures of this type and dilutions of this type can be used significantly as marker signals as single-point measurements, down to dilutions of 0.0080%, and indeed even lower by using the entire spectral information.

Example 11

Irradiation of activated samples with X-rays

Irradiation of the sample

In each case an aliquot of 1g of sample was weighed out and the irradiation was carried out by X-ray irradiation from a rhodium X-ray tube. This was done using an Axios DY1402 x-ray fluorescence spectrometer (Malvern Panalytical GmbH, Kassel, Germany). The current intensity was 66mA and the voltage was 60 kV. The sample was thus exposed to a power of 3960W. The irradiation times were 20, 30 and 40 seconds, respectively. The compounds tested were as follows:

lactose monohydrate (20 seconds, 30 seconds, 40 seconds)

PVP (Kollidon 30) (20 sec, 30 sec, 40 sec)

·

L100 (20 seconds, 30 seconds, 40 seconds)

Diamond powder (20 seconds, 30 seconds, 40 seconds)

Ink (black, white) (40 seconds)

D (-) -mannitol (20 seconds, 30 seconds, 40 seconds)

HPMC (20 seconds, 30 seconds, 40 seconds)

Zirconium (IV) oxide (20 sec, 30 sec, 40 sec)

Titanium dioxide (20 seconds, 30 seconds, 40 seconds)

Polylactide-co-glycolide (20 seconds, 30 seconds, 40 seconds)

Protein (triple helix collagen) (20 sec, 30 sec, 40 sec)

At the doses and wavelengths used, the individual compounds lactose monohydrate and D (-) -mannitol exhibit new resonance intensities that are linear over a wide range depending on the dose. The spectrum is significant and the substances can be mixed arbitrarily. As sugars, they are suitable for use in foods and pharmaceuticals. In contrast, titanium oxide changes its pattern due to irradiation and can therefore also be functionally used according to the invention as an internal marker. Titanium dioxide is also unobjectionable in that,and are widely used as fillers and pigments. In contrast, no spectral changes of the species detected with other polymers were detected with the zirconia, PVP and diamond powders at the energy pulse level with the rhodium source.

L100 shows the characteristic property of rapidly generating quantitative signal saturation after X-ray irradiation (described). This effect (internal standard) may result from trace amounts of the polymer product component that upon irradiation is quasi-quantitatively increased to ESR-visible modification. This type of functional uniqueness is dramatic, specific, and thus functionally desirable for the markers according to the present invention. HPMC and cellulose-based polymers have not been partially modified in an ESR-visible manner by this method (described). However, a minimum signal on the order of magnitude of the noise limit of the unoptimized method shows the possibility of intrinsic labeling by illumination.

Example 12

Finally, all the signal-providing mixtures used here and the single substance of example 11 subjected to measurement were combined into a single representation (fig. 15). This shows the widespread use of the technically available spectral range (energy range of resonance, here indicated in the usual way (magnetic flux density, B, in mT)). The signal width is also very different depending on the label and can be used for specificity of signal recognition. The signal is significantly higher than noise over a very wide dynamic range and can be easily typified and identified in all dilutions used here in an automated manner by spectral simulation, spectral principal component analysis and by learning routines (neural/deep learning pattern recognition/and artificial intelligence methods, fingerprint peak picking B, B frequency normalization pattern, g-factor normalization). The significant but weaker spectral components of MgO (magnesium (II) oxide) are identified here by means of eye failure, i.e. baseline resolution and baseline correction are not necessary for these new statistical mathematical methods. This method cannot be quantitatively implemented not only in terms of process requirements, purity and environmental conditions but also in the dynamic range.

With this spectral simulation of the actual single spectrum measured by modification of the above identified compounds and irradiated samples, the experiments performed showed dynamics extending into the picogram range of signal identification without a dedicated method and without any sample preparation. The channel specificity conferred by the significant signal form suggests a code channel depth of at least 50-100 in the sense of measuring size (-characteristic features or positions of bar "codes). Without special procedures, the measurement sensitivity here is picograms per gram of sample. By using the transmission power and the characteristic feature width and simple height of the measurement method in signal acquisition, the method can be widely used in the femtogram range.

The method can be used in particular in fields where physical properties, health quality and environmental quality are not adversely affected in any way.

Claims

1. Product with a blend of identification substances comprising a paramagnetic phase and having an ESR fingerprint allowing to unambiguously identify the product.

2. The product of claim 1, wherein the paramagnetic phase of the identification substance blend is formed from one or more phases selected from the group consisting of:

polymers with paramagnetic centers, preferably with isolated radicals,

-molecular paramagnets, and

paramagnetic phase of mineral substances and/or salts, especially Al₂O₃、SiO₂Natural or artificially doped diamond or ZrO₂The paramagnetic phase of (a).

3. The product according to claim 1 or 2, wherein the paramagnetic phase of the identification substance blend is produced by a method comprising coating, blending, doping, sputtering, chemical radical generation and/or irradiation.

4. The product of any of claims 1-3, wherein the resonance frequency, line shape, intensity, signal coupling, and/or spatial variation in the ESR fingerprint is evaluable.

5. The product according to any of claims 1 to 4, wherein the ESR fingerprint is mechanically and/or thermally stable.

6. The product according to any of claims 1-5, wherein the product is a pharmaceutical (drug), a food or beverage product or a precursor or intermediate or defined constituent thereof, such as a package, blister pack, container or the like.

7. The product according to any of claims 1-5, wherein the product is a fabric, textile or leather product, a coin, a banknote, a security, a document, a certificate or cheque card or chip card or part thereof, a gemstone or semi-gemstone, a medical product, an implant or graft, or a replacement part or supplier part of an industrial product.

8. The product according to any of claims 1 to 7, wherein the ESR fingerprint encodes the manufacturer, the place of manufacture, the time of manufacture, and/or the product itself or production specific data (intended use, rights, etc.).

9. The product of any of claims 1-8, wherein a defined product batch of the product comprises the same blend of identification substances.

10. A method of producing a clearly identifiable product, comprising the method step of applying to or incorporating into the product a blend of an identification substance comprising a paramagnetic phase and having an ESR fingerprint allowing the product to be clearly identified.

11. The method of claim 10, wherein the paramagnetic phase of the identification substance blend is formed from one or more phases selected from the group consisting of:

polymers with paramagnetic centers, preferably with isolated radicals,

-molecular paramagnets, and

12. The method of claim 10 or 11, wherein the paramagnetic phase of the identification substance blend is produced by a process comprising coating, blending, doping, sputtering, chemical radical generation and/or irradiation, printing, embossing, melting, extrusion, pressing, pelletizing, spheronizing, spray drying, additive manufacturing, thermal transfer, thermal embossing, laser methods, ink jet printing, and holographic printing.

13. The method of any one of claims 10-12, wherein the product is a pharmaceutical, food or beverage product or a precursor or intermediate thereof.

14. The method according to any one of claims 10-12, wherein the product is a fabric, textile or leather product, a banknote, a cheque card, a gemstone or semi-gemstone, a medical product, or a replacement part or a supplier part of an industrial product.

15. The product authentication method comprises the following steps:

(a) applying or introducing into/into a product an identification substance blend comprising a paramagnetic phase, or identifying a product comprising an identification substance blend comprising a paramagnetic phase, said identification substance blend having an ESR fingerprint allowing unambiguous identification of said product,

(b) recording the ESR fingerprint of the product,

(c) generating and storing a digital representation of the ESR fingerprint,

(e) verifying the product to be authenticated by comparing the digital representation of the measured ESR spectrum of the product to be authenticated with a digital representation of a stored ESR fingerprint spectrum.

16. The method of claim 15, wherein the digital representation of an ESR fingerprint comprises a hash value derived from the ESR fingerprint.

17. The method of claim 15 or 16, wherein the digital representation of the ESR fingerprint spectrum assigned to a product is stored in a blockchain network in an anti-counterfeiting and anti-manipulation manner.

18. The method of claim 17, wherein for each stored digital representation of the ESR fingerprint, a distinct non-replaceable token is generated across the blockchain network.

19. The method according to any of claims 15 to 18, wherein the verification of the authenticity of the plurality of measured ESR spectra is performed in a common detection step.

20. The method according to any of claims 15-19, wherein method step (d) is performed with a mobile terminal device, preferably a smartphone, on which a computer program is executed for measuring the ESR map of the product using circuit components of the mobile terminal device.

21. The method of claim 20, wherein the ESR pattern of the product is measured using an additional permanent magnet or antenna or external switchable circuit component suitable for the purpose.

22. Method for verifying the authenticity of a product having an identification substance blend comprising a paramagnetic phase and having an ESR fingerprint allowing the product to be unambiguously identified, having the following method steps:

-recording the ESR map of the product with a mobile terminal device, preferably a smartphone, executing on the mobile terminal device a computer program for measuring the ESR map of the product using circuit components of the mobile terminal device, and

-comparing the recorded ESR spectrum of the product with a stored ESR fingerprint spectrum.

23. The method of claim 22, wherein the ESR pattern of the product is measured using an additional permanent magnet.

24. Device for authenticating a product having an identification substance blend comprising a paramagnetic phase and having an ESR fingerprint allowing unambiguous identification of the product, wherein the device has:

a spectrometer unit arranged to measure an ESR spectrum,

-a communication unit arranged to access a database storing a digital representation of ESR fingerprint spectra, an

-a data processing unit arranged to create a digital representation of the measured ESR fingerprint of the product to be authenticated and to compare it with the digital representation of the ESR fingerprint spectrum stored in the database.

25. Device according to claim 24, in the form of a mobile terminal device or a fixed terminal device, preferably in the form of a smartphone, on which a computer program for measuring the ESR map of the product using circuit components of the mobile terminal device is executable.

26. Use of a mobile terminal device, preferably a smartphone, for authenticating a product comprising an identification substance blend comprising a paramagnetic phase and having an ESR fingerprint, on which a computer program is executed for measuring the ESR spectrum of the product using circuit components of the mobile terminal device.

27. A computer program product executable on a terminal device, preferably a smartphone, which when executed on the terminal device uses circuit components of the terminal device to measure an ESR map of a sample comprising a paramagnetic phase.